Sulfated fatty urea nu-glycosides



Patented Oct. 1, 1957 ice 2,808,404 SULEATED FATTY UREA N-errcosronsJohn G. Erickson, Minneapolis, Minn., assignor to General Mills, Inc., acorporation of Delaware No Drawing. Application May 11, 1953, Serial N0.354,417

5 Claims. (Cl. 260-2115) The present invention relates to sulfationproducts of fatty urea N-glycosides. These products are obtained by thesulfation of the reaction products of fatty ureas with aldose sugars.Typical products obtainable with aldohexoses include the following:

O O RNHiiNHOHOHOHCHOHCHCHCHaOSOaM OSOQM 0803M OS OaM OSOaM OSOaM inwhich R is a long chain aliphatic hydrocarbon group containing from 8-22carbon atoms and M is alkali metal or ammonium. These compounds areuseful as emulsifiers and wetting agents, detergents and the like.

It is, therefore, an object of the present invention to provide novelcompounds derived by the sulfation of reaction products of fatty ureasand aldose sugars.

These compounds may be prepared by first reacting fatty amines with ureato obtain a fatty urea which'is then reacted with an aldose sugar toform the fatty urea N-glycosides. These glycosides are then sulfated toform the products of the present invention. The fatty amines which maybe used are the primary fatty amines containing from 8-22 carbon atoms.They may be the mixed amines prepared from the mixed acids of a fat oroil or from any isolated single fatty acid or any particular group offatty acids. Thus the fatty group in the ultimate product may :be eithersaturated or unsaturated. Typical fatty groups include octyl decyl,dodecyl, tetradecyl, hexadecyl, octadecyl, etc.

Any aldose may be used for reaction with the fatty urea. Since the'aldohexoses and aldopentoses are the most readily available, they arepreferred. Typical aldoses include glucose, galactose, mannose,arabinose, lyxose, xylose, ribose and the like. The reaction between thealdose and the fatty urea is preferably carried out in the presence of asmall quantity of mineral acid and in the presence of ethanol as asolvent. Reaction temperatures of around 50 C. for 50-60 hours aresuitable.

The fatty urea N-glycoside thus formed is then reacted with any suitablesulfating agent such as sulfur trioxide, chlorosulfonic acid or sulfuricacid. The reaction is carried out in a solvent which is inert to thereactants such as carbon tetrachloride, chloroform, tetrachloroethaneand so forth. The reaction may be carried out at temperatures from 10 C.to 100 C. Preferred temperatures are from 15-50 C. It is known thatstrong acids tend to cause discoloration, darkening and decomposition ofsugar compounds. Notwithstanding this fact, it has been observed thatthere appears to be no decomposition of the sugar residue during thisreaction. The products obtained are white or very faintly tinged withyellow. After thesulfation reaction, it is desirable to neutralize theacid sulfate ester. This is done by adding a suitable alkaline materialsuch as sodium or potassium hydroxides, carbonates or acetates, ammoniumhydroxide and the like.

The number of sulfate groups introduced into the molecule is determinedby regulating the amount of sulfating agent employed. In general, themolar ratio of sulfating agent to glycoside is approximately equal tothe "number of sulfate groups to be introduced.

All of these compounds possess wetting, cleansing and detergentproperties. With the shorter chain fatty groups, for example, thosecontaining from 8-12 carbon atoms,best results are obtained with asingle sulfate group. Where the fatty group contains 18-22 carbon atoms,it is preferred to introduce 3 or 4 sulfate groups. At intermediatecarbon chain lengths, two sulfate groups are desirable.

EXAMPLE 1 A solution of 0.69 part of chlorosulfonic acid in 22 parts ofchloroform was added to a suspension of 1.95 parts of dodecylureaN-galactoside in parts of chloroform at 25 C. The mixture becamehomogeneous. After ten minutes, it was made alkaline with a solution ofsodium hydroxide in aqueous alcohol. It was then made slightly acidicwith acetic acid and allowed to evaporate. This left a very light yellowsolid as residue. This was the sodium salt of the monosulfate ofdodecylurea N- galactoside. It dissolved readily in water, giving asolution which foamed very well.

The compound was tested for foaming and for detergency as a 0.1% aqueoussolution, pH 9.0.

Ross-Miles foam test (25 C.)

Initial height Height after 5 min. (min) Detergency (increase inreflectance, expressed as percent: MgO

Compound Percent Sodium dodecylurea N-galaetoside monosulfate 5. 1Commercial sample of sodium dodecylbenzenesulfonate. 24. 9

3 EXAMPLE 2 A mixture of 6.2 parts of octadecylurea, 4.0 parts ofglucose, 0.5 part of concentrated hydrochloric acid and 80 partsof 95%ethanol was stirred and heated to 50 Cfifor 147.5 ,hours. It .was thencooled and filtered, yielding a white solid. This was washed with hotbenzene to give octadecylurea N-glucoside, M. P. 175188 C. withdecomposition. V

A solution of 0.35 part of chlorosulfonic acid in 15 parts of chloroformwas added to a suspension of 0.47 part of octadecylurea N-glucoside in37 parts of chloroform. The solid dissolved rapidly. After '20 minutes,

the mixture was made slightly basic with an aqueousalcoholic solution ofpotassium hydroxide, then made acidic with a drop of acetic acid. Themixture was allowed to evaporate, leaving a White solid as residue. Itwas the tripotassium salt of the trisulfate of octadecylureaiN-glucoside. Aqueous solutions of this product showed surface-"activeproperties.

Numerous-other products coming within the scope of the present inventionmay be made according to the above examples by substituting fatty ureaN-glycosides derived from other aldoses and other fatty amines. Thereaction conditions are essentially the same and the products obtainedvary in their properties as described above.

I claim as my invention:

1. A sulfated fatty urea N- glycoside in which the fatty group containsfrom 8-22 carbon atoms.

2. A sulfated fatty urea N-galactoside in which the fatty group containsfrom 8-22 carbon atoms.

3. A sulfated fatty urea N-glucoside in which the fatty group containsfrom 8-22 carbon atoms.

4. The sodium salt of the monosulfate of dodecylurea N-galactoside.

5. The tripotassium salt of the trisulfate of octadecylurea N-glueoside.

References Cited in the file of this patent UNITED STATES PATENTS2,002,613 Orthner et a1 May 28, 1935 2,596,268 Meijer May 13, 19522,599,172 Hadidian June 3, 1952 2,612,497 Meijer Sept. 30, 19522,612,499 Pulver "Sept. 30, 1952 OTHER REFERENCES Hudson et al.:Advances in Carbohydrate Chemistry, vol. 8, published by Academic Press(New York), 1953 (pages 116 and 117).

1. A SULFATED FATTY UREA N-GLYCOSIDE IN WHICH THE FATTY GROUP CONTAINSFROM 8-22 CARBON ATOMS.